WO2019026848A1 - 光電変換装置 - Google Patents

光電変換装置 Download PDF

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Publication number
WO2019026848A1
WO2019026848A1 PCT/JP2018/028467 JP2018028467W WO2019026848A1 WO 2019026848 A1 WO2019026848 A1 WO 2019026848A1 JP 2018028467 W JP2018028467 W JP 2018028467W WO 2019026848 A1 WO2019026848 A1 WO 2019026848A1
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WO
WIPO (PCT)
Prior art keywords
photoelectric conversion
optical filter
conversion device
resin
resin layer
Prior art date
Application number
PCT/JP2018/028467
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English (en)
French (fr)
Japanese (ja)
Inventor
拓也 三浦
大吾 一戸
Original Assignee
Jsr株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr株式会社 filed Critical Jsr株式会社
Priority to CN201880048586.5A priority Critical patent/CN110945665B/zh
Priority to JP2019534503A priority patent/JPWO2019026848A1/ja
Priority to KR1020207002552A priority patent/KR102562643B1/ko
Publication of WO2019026848A1 publication Critical patent/WO2019026848A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0232—Optical elements or arrangements associated with the device
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to an optical filter and a photoelectric conversion device having the optical filter.
  • CCD and CMOS image sensors that are solid-state imaging devices for color images are used for solid-state imaging devices mounted on video cameras, digital still cameras, portable terminals with camera functions, and the like.
  • silicon photodiodes having sensitivity to near infrared rays that can not be detected by human eyes in the light receiving portion are used.
  • an optical filter for example, near
  • Infrared cut filters, near infrared transmission filters are often used.
  • an illumination sensor and an ambient light sensor are mounted on the portable terminal, and such an illumination sensor and the ambient light sensor acquire light as in the solid-state imaging device.
  • the illuminance sensor or the ambient light sensor can control the brightness of the image of the portable terminal based on the acquired light.
  • the solid-state imaging device, the illuminance sensor, and the environment sensor have a function of converting light into an electric signal, and are called a photoelectric conversion device.
  • Patent Document 1 discloses a near-infrared cut filter in which a transparent resin is used as a base material and a near-infrared absorbing dye is contained in the transparent resin
  • Patent Document 2 discloses a near-infrared transmission filter.
  • Patent Document 3 as an optical filter, a method of manufacturing by bonding a glass substrate and an infrared cut filter substrate with an adhesive, or a film forming process on a cover glass, an infrared cut filter layer is formed. Methods of forming are disclosed.
  • the image quality level required for camera images has become extremely high also in mobile devices and the like.
  • near-infrared cut filters used in solid-state imaging devices high visible light transmittance and high light-cut characteristics in the near-infrared wavelength range are required.
  • high near-infrared wavelength region transmittance and high ray cut characteristics in the visible light wavelength region are required.
  • the heat resistance performance of the employed dye is not sufficient.
  • the near-infrared absorbing dye of the near-infrared cut filter is decomposed, which may cause a problem in the long-term reliability of the near-infrared cut filter.
  • the similar problem of heat resistance of the dye is also apparent in the near infrared transmission filter.
  • an object of the present invention is to provide an optical filter excellent in heat resistance. Another object is to provide a photoelectric conversion device having an optical filter with excellent heat resistance.
  • a photoelectric conversion device includes a photoelectric conversion element provided on a semiconductor substrate and an optical filter provided on the photoelectric conversion element, and the optical filter has a thermal decomposition start temperature of 150. °C and the resin layer containing the above pigment, comprising a layer for protecting the photoelectric conversion element, the dynamic hardness of the resin layer of the optical filter is 10 mN / [mu] m 2 or more 150 mN / [mu] m 2 or less.
  • a photoelectric conversion device includes a photoelectric conversion element provided on a semiconductor substrate and an optical filter provided on the photoelectric conversion element, and the optical filter has a dynamic hardness of 10 mN / ⁇ m.
  • the photoelectric conversion device which has a resin base material which is 2 or more and 150 mN / ⁇ m 2 or less, satisfies the following (A) and (B), and contains a dye having a thermal decomposition start temperature of 150 ° C. or more.
  • (A) The average transmittance in the wavelength range of 430 nm to 580 nm is 75% or more.
  • B The average transmittance in the wavelength range of 700 nm to 800 nm is 20% or less.
  • a photoelectric conversion device includes a photoelectric conversion element provided on a semiconductor substrate and an optical filter provided on the photoelectric conversion element, and the optical filter has a dynamic hardness of 10 mN / ⁇ m.
  • the photoelectric conversion device which has a resin base material which is 2 or more and 150 mN / ⁇ m 2 or less, satisfies the following (A) and (B), and contains a dye having a thermal decomposition start temperature of 150 ° C. or more.
  • A The average transmittance in the wavelength range of 400 nm to 730 nm is 2% or less.
  • B The average transmittance in the wavelength range of 800 nm to 1000 nm is 80% or more.
  • the electronic device is a device having a function of performing digital processing or analag processing of various information including video and audio, and includes an electrical product to which a technology belonging to electronic technology is applied.
  • an optical filter having excellent heat resistance can be provided.
  • a photoelectric conversion device having an optical filter with excellent heat resistance can be provided.
  • upper refers to a relative position based on the main surface (the surface on which the photoelectric conversion element is disposed) of the support substrate, and the direction away from the main surface of the support substrate is “upper”. .
  • the upper side is “up” toward the paper surface.
  • “upper” includes the case of touching the top of the object (that is, in the case of “on”) and the case of being positioned above the object (that is, in the case of “over”).
  • “below” refers to a relative position with respect to the main surface of the support substrate, and the direction approaching the main surface of the support substrate is “down”. In the drawings of the present application, the lower side is “down” toward the paper surface.
  • an optical filter according to an embodiment of the present invention and a photoelectric conversion device having the optical filter will be described with reference to FIGS. 1 to 5.
  • a solid-state imaging device will be described as an example of the optical conversion device.
  • the solid-state imaging device is an image sensor provided with a solid-state imaging device such as a CCD or a CMOS image sensor.
  • the solid-state imaging device can be used for digital still cameras, cameras for smartphones, cameras for mobile phones, cameras for wearable devices, digital video cameras, and the like.
  • FIG. 1 shows a cross-sectional view of the photoelectric conversion device 116 according to the present embodiment.
  • the photoelectric conversion device 116 includes a semiconductor substrate 112 provided with the photoelectric conversion element 113, an optical filter 103 provided on the photoelectric conversion element 113, and an optical low pass filter 115.
  • CCDs charge coupled devices
  • a CMOS image sensor can be used instead of the CCD image sensor.
  • a plurality of terminals are provided at the edge of the upper surface of the semiconductor substrate 112.
  • the plurality of terminals are connected to the plurality of photoelectric conversion elements 113 through the wirings formed on the upper surface of the semiconductor substrate 112. Further, the plurality of terminals are connected to the support substrate 111 by the wires 114.
  • An optical filter 103 according to the present embodiment is provided on the photoelectric conversion element 113, and an optical low pass filter 115 is provided on the optical filter 103.
  • the structure of the optical filter 103 will be described in detail later.
  • the camera module 110 further includes a photoelectric conversion device 116, a lens 117, and a package 118.
  • the optical filter 103 and the optical low pass filter 115 are held by the package 118.
  • the package 118 is formed of a ceramic material such as alumina, a metal material, or a plastic material. Further, the package 118 has a region in which the photoelectric conversion device 116 is accommodated, and a lens barrel portion that holds the lens 117, and is fixed to the support substrate 111.
  • the thinned optical filter 103 for the photoelectric conversion device 116, the height of the photoelectric conversion device 116 and the camera module 110 can be reduced. Further, by providing the optical filter 103 and the optical low pass filter 115, the imaging quality of the photoelectric conversion device 116 can be improved.
  • the optical filter 103 When the package 118 provided with the optical filter 103 is provided on the support substrate 111, high temperature may be applied to the optical filter 103. Since the optical filter 103 according to the present embodiment has heat resistance, deterioration of the optical filter 103 in the reflow process can be suppressed.
  • the optical filter 103 according to the present embodiment can be thinned.
  • the optical filter 103 is used for a lens unit such as a camera module, the height and weight of the lens unit can be reduced.
  • FIG. 2 shows the configuration of the optical filter 103 according to the present embodiment.
  • the optical filter 103 according to the present embodiment has a base 101 and a resin layer 102.
  • the resin layer 102 contains a dye or the like that absorbs infrared light.
  • the resin layer 102 contains a dye that absorbs light in the visible region.
  • a translucent substrate is used.
  • the base material 101 has a function which protects a photoelectric conversion element.
  • the base material 101 is adhered to the package 118 with various adhesives, protects the photoelectric conversion element 113 housed inside the package 118, and functions as a light transmission window for visible light and the like. is there.
  • a colorless and transparent glass substrate is preferably used.
  • a colorless and transparent glass substrate for example, the cover glass described in JP-A-2004-221541, JP-A-2006-149458, etc. can be used.
  • the protective layer is not limited to the glass substrate, and a transparent organic resin may be used.
  • a transparent resin can be used as the organic resin.
  • the base material 101 for example, a glass substrate or a resin substrate can be used.
  • the thickness of the substrate 101 is 0.01 mm or more and 2 mm or less, preferably 0.05 mm or more and 1 mm or less.
  • the thickness of the glass substrate is in the above range, the weight and size of the optical filter 103 can be reduced.
  • the thickness of the base material 101 is thicker than the above, the height of the photoelectric conversion device and the camera module can not be reduced.
  • the thickness of the substrate 101 is smaller than the above range, the warpage of the optical filter 103 becomes large.
  • the base material 101 may be broken or chipped because it becomes brittle.
  • a resin layer 102 is provided on the base material 101.
  • the resin layer 102 is provided on at least one surface of the base material 101.
  • the resin layer 102 preferably has a dynamic hardness higher than that of the substrate 101.
  • the dynamic hardness of the resin layer 102 is preferably 10 mN / [mu] m 2 or more 150 mN / [mu] m 2 or less.
  • the strength of the resin layer 102 can be secured.
  • the dynamic hardness of the resin layer 102 is lower than the above range, the resin layer 102 may be broken or chipped.
  • the resin layer is easily peeled off.
  • the dynamic hardness of the resin layer 102 can be measured, for example, with a microhardness tester.
  • the dynamic hardness is obtained by dividing the load when the triangular pyramid diamond indenter with a gap angle of 115 ° is pushed into the film surface by the square of the pushing depth while gradually applying a load at a constant load rate. It is expressed by the calculated dynamic hardness (DH), and is defined by the following equation (1).
  • DH ⁇ P / D 2 (1)
  • P Load (gf)
  • D Indentation depth ( ⁇ m)
  • the dynamic hardness of the resin layer 102 described above is measured using a Shimadzu dynamic ultra-microhardness tester (model DUH-201s, manufactured by Shimadzu Corporation), measurement mode: MODE5, indentation depth 1 ⁇ m, indentation speed 0.014 mN / It can be obtained by measuring under the condition of s and converting according to the above-mentioned formula.
  • the dynamic hardness of the resin layer 102 is 10mN / ⁇ m 2 ⁇ 150mN / ⁇ m 2. If the dynamic hardness is less than 10 mN / ⁇ m 2 , the resin layer may be cracked or part of the resin layer may be chipped. On the other hand, when the dynamic hardness is more than 150 mN / ⁇ m 2 , the film is likely to peel off the glass substrate.
  • the transmittance of the optical filter 103 preferably satisfies the following (A) and (B).
  • A) The average value of the transmittance in the wavelength range of 430 nm to 580 nm is preferably 75% or more.
  • the average transmittance in this wavelength range is in this range, near infrared rays can be sufficiently cut when the near infrared cut filter (optical filter 103) is used as a photoelectric conversion device application, and excellent color reproducibility is obtained. It is preferable because it can be achieved.
  • the transmittance of the optical filter 103 preferably satisfies the following (A) and (B).
  • visible light can be sufficiently cut when the near infrared transmission filter (optical filter 103) is used as a photoelectric conversion device application, and excellent infrared sensing can be achieved. It is preferable because it can be achieved.
  • the resin layer 102 contains the pigment
  • dye whose thermal decomposition start temperature is 150 degreeC or more.
  • an infrared cut filter as an infrared absorbing organic dye, for example, cesium tungsten oxide, metal boride, titanium oxide, zirconium oxide, tin-doped indium oxide, antimony-doped tin oxide, azo compound, aminium compound, iminium compound, anthraquinone compound, One kind of compound among cyanine compounds, diimonium compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, anthraquinone compounds, naphthoquinone compounds, dithiol compounds and polymethine compounds can be used. As specific examples of such compounds, compounds described in WO 2011/118171 and JP-A 2013-195480 can be used.
  • cesium tungsten oxide is preferable because of its high infrared absorption ability and thermal decomposition temperature. Also, it can be used in combination with organic pigment compounds such as dimonium compounds, squarylium compounds, phthalocyanine compounds and naphthalocyanine compounds.
  • the content of such a dye is preferably 20% by mass to 85% by mass, and preferably 30% by mass to 80% by mass, with respect to the total solid mass of the resin composition forming the resin layer. More preferably, the content is 40% by mass to 75% by mass.
  • a black dye in the case of an infrared transmitting filter, as such a dye, a black dye can be mentioned, and for example, dyes such as azo dyes, anthraquinone dyes, perinone dyes, perylene dyes, methine dyes, quinoline dyes and azine dyes can be exemplified. .
  • azo dyes include C.I. I. Solvent yellow 14, C.I. I. Solvent yellow 16, C.I. I. Solvent yellow 21, C.I. I. Solvent yellow 61, C.I. I. Solvent yellow 81, C.I. I. Solvent red 1, C.I. I. Solvent red 2, C.I. I. Solvent red 8, C.I. I. Solvent red 19, C.I. I. Solvent red 23, C.I. I. Solvent red 24, C.I. I. Solvent red 27, C.I. I. Solvent red 31, C.I. I. Solvent red 83, C.I. I. Solvent red 84, C.I. I. Solvent red 121, C.I. I.
  • Solvent red 132 C.I. I. Solvent violet 21, C.I. I. Solvent black 3, C.I. I. Solvent black 4, C.I. I. Solvent black 21, C.I. I. Solvent black 23, C.I. I. Solvent black 27, C.I. I. Solvent black 28, C.I. I. Solvent black 31, C.I. I. Solvent orange 7, C.I. I. Solvent orange 9, C.I. I. Solvent orange 37, C.I. I. Solvent orange 40, C.I. I. Solvent Orange 45 etc. are mentioned.
  • anthraquinone dyes include C.I. I. Solvent red 52, C.I. I. Solvent red 111, C.I. I. Solvent red 149, C.I. I. Solvent red 150, C.I. I. Solvent red 151, C.I. I. Solvent red 168, C.I. I. Solvent red 191, C.I. I. Solvent red 207, C.I. I. Solvent blue 35, C.I. I. Solvent blue 36, C.I. I. Solvent blue 63, C.I. I. Solvent blue 78, C.I. I. Solvent blue 83, C.I. I. Solvent blue 87, C.I. I. Solvent blue 94, C.I.
  • perinone dyes include C.I. I. Solvent orange 60, C.I. I. Solvent orange 78, C.I. I. Solvent orange 90, C.I. I. Solvent violet 29, C.I. I. Solvent red 135, C.I. I. Solvent red 162, C.I. I. Solvent Orange 179 and the like.
  • perylene dyes include C.I. I. Solvent green 5, C.I. I. Solvent orange 55, C.I. I. Butt Red 15, C.I. I. Bat orange 7 etc. are mentioned.
  • methine dyes include C.I. I. Solvent orange 80, C.I. I. Solvent Yellow 93 and the like.
  • quinoline dyes include C.I. I. Solvent yellow 33, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 157 and the like.
  • azine dyes include C.I. I. Solvent black 5, C.I. I. Solvent Black 7 etc. are mentioned.
  • the use of an azo dye having a large absorption coefficient and high solubility is preferable. From the viewpoint of environmental conservation, those containing no halogen element in the molecule are preferable.
  • the content of such a dye is preferably 20% by mass to 85% by mass, and preferably 30% by mass to 80% by mass, with respect to the total solid mass of the composition forming the resin of the present invention. Is more preferable, and 40% by mass to 75% by mass is more preferable.
  • a green pigment in addition to the black pigment, a green pigment can also be added.
  • a green dye include squarylium dyes, phthalocyanine dyes, and cyanine dyes. From these dyes, one or more can be appropriately selected and used according to the application and the like.
  • the green dye may be a pigment in which molecules are aggregated in a transparent resin as described later, but a green dye in which molecules are dissolved in a transparent resin is preferable because it is less likely to cause scattered light. .
  • squarylium dyes and phthalocyanine dyes are particularly preferable.
  • the squarylium dye is preferably one having an absorption maximum wavelength within a wavelength of 600 nm to 800 nm in the absorption spectrum of light having a wavelength of 400 nm to 1000 nm measured using a resin film obtained by dispersing in a transparent resin. Further, it is preferable that the slope on the infrared light side of the absorption peak at which the absorption maximum wavelength appears is steep.
  • the phthalocyanine dye is preferably one having an absorption maximum wavelength within a wavelength of 700 nm to 900 nm in the absorption spectrum of light having a wavelength of 400 nm to 1000 nm measured using a resin film obtained by dispersing in a transparent resin. Further, it is preferable that the slope on the infrared light side of the absorption peak at which the absorption maximum wavelength appears is steep.
  • the green pigment may be a dye in which molecules are dissolved in a transparent resin, or a pigment in which molecules are aggregated in a transparent resin. If a pigment is used as the green pigment, dispersants can also be used. As a dispersing agent, dispersing agents such as cationic type, anionic type and nonionic type can be used.
  • the resin layer 102 containing a pigment is formed of a resin composition in which the pigment and the transparent resin are mixed.
  • the transparent resin preferably has a glass transition temperature (Tg) of 0 ° C. to 380 ° C.
  • Tg glass transition temperature
  • the lower limit of Tg is more preferably 40 ° C. or more, still more preferably 60 ° C. or more, still more preferably 70 ° C. or more, and particularly preferably 100 ° C. or more.
  • the upper limit of Tg is more preferably 370 ° C. or less, and still more preferably 360 ° C. or less.
  • the transparent resin examples include polyester resin, polyether resin, acrylic resin, polyolefin resin, cyclic olefin resin, polycarbonate resin, ene / thiol resin, epoxy resin, polyamide resin, polyimide resin, polyamide imide resin, polyurethane resin, polystyrene Resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyparaphenylene resin, polyarylene ether phosphine oxide resin, etc. may be mentioned.
  • acrylic resin, polyester resin, polycarbonate resin, or cyclic olefin resin is preferable.
  • polyester resin polyethylene terephthalate resin, polyethylene naphthalate resin, etc. are preferable.
  • the transparent resin may be a polymer alloy in which a plurality of different resins are combined.
  • the transparent resin may be a resin having a high molecular weight in advance, or may be a resin to which a low molecular weight substance is applied and which is polymerized (high molecular weight) and cured by energy rays such as heat or ultraviolet light.
  • a commercially available product may be used as the transparent resin.
  • acrylic resin Ogsol (registered trademark) EA-F 5003 (Osaka Gas Chemical Co., Ltd. product name), polymethyl methacrylate, polyisobutyl methacrylate, BR50 (Mitsubishi Rayon Co., Ltd. product name) Etc.
  • polyester resins OKPH4HT, OKPH4, B-OKP2, OKP-850 (all of which are trade names by Osaka Gas Chemical Co., Ltd., trade names), Byron (registered trademark) 103 (trade names, by Toyobo Co., Ltd.)
  • polycarbonate resins LeXan (registered trademark) ML9103 (sabic, trade name), EP 5000 (Mitsubishi Gas Chemical Co., Ltd., trade name), SP3810 (Teijin Chemicals, Ltd., trade name), SP1516 (trade name) Teijin Kasei Co., Ltd. product name, TS2020 (Teijin Kasei Co., Ltd. product name, trade name), xylex (registered trademark) 7507 (sabic company, trade name), etc. are mentioned.
  • cyclic olefin resin As cyclic olefin resin, ARTON (registered trademark) (made by JSR Corporation, trade name, Tg: 165 ° C), ZEONEX (registered trademark) (made by Nippon Zeon, trade name, Tg: 138 ° C), etc. Can be mentioned.
  • a resin composition when apply
  • a compound having a group and a polymerization initiator As such a compound having a polymerizable group and a polymerization initiator, known compounds can be used, and for example, compounds described in JP-A-2013-195480, WO2016 / 098810, etc. can be used. it can.
  • a color tone correction pigment for example, a color tone correction pigment, a leveling agent, an antistatic agent, a heat stabilizer, a light stabilizer, an antioxidant, a dispersant, a flame retardant, a lubricant, a plasticizer, transparent nanoparticles Etc.
  • a dispersion medium which can stably disperse the raw material component of the transparent resin, and each component which is blended as needed, or a solvent which can dissolve it.
  • solvent the following solvents may be mentioned.
  • Alcohols such as isopropyl alcohol, n-butyl alcohol, ethyl cellosolve, methyl cellosolve, glycols such as ethylene glycol, diethylene glycol, propylene glycol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, N, N- Amides such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol monomethyl ether, ethylene glycol monoethylene ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol butyl ether, Ethylene
  • the resin layer is formed by applying the resin composition onto a substrate and then drying it.
  • known methods such as heat drying and hot air drying can be used.
  • curing treatment is further performed.
  • the reaction is heat curing, drying and curing can be carried out simultaneously, but in the case of light curing, a curing step can be provided separately from drying.
  • the thickness of such a resin layer 102 is 0.1 ⁇ m to 3 ⁇ m, preferably 0.5 ⁇ m to 2 ⁇ m.
  • the thickness of the resin layer 102 is in the above range, the weight and size of the optical filter 103 can be reduced, and reduction in height of the photoelectric conversion device 116 can be achieved.
  • the thickness of the resin layer 102 is thicker than the above range, the height of the photoelectric conversion device and the camera module can not be reduced.
  • the thickness of the resin layer 102 is thinner than the above range, there is a problem that the warpage of the optical filter becomes large.
  • the infrared ray absorption performance of the resin layer 102 is reduced.
  • a dielectric multilayer film may be provided on at least one surface of the substrate 101.
  • the dielectric multilayer film may be provided in contact with the base material 101 or may be provided on the base material 101 via the resin layer 102.
  • the manufacturing cost and the ease of manufacturing are excellent.
  • the dielectric multilayer film is provided on both sides of the base material 101, it is possible to obtain the optical filter 103 which has high strength and is not easily warped or twisted.
  • the optical filter 103 is applied to a photoelectric conversion device or the like, it is preferable to provide a dielectric multilayer film on both sides of the substrate 101 because it is preferable that the optical filter 103 have small warpage or twist.
  • the optical filter 103 When the optical filter 103 is used as a near infrared cut filter, the optical filter 103 preferably satisfies the following (A) and (B).
  • the average transmittance in these wavelength ranges is in this range, near infrared rays can be sufficiently cut when the near infrared cut filter (optical filter 103) is used as a photoelectric conversion device application, and excellent color reproducibility Is preferable because it can achieve the
  • the resin layer 102 contains the infrared rays absorption organic pigment
  • the optical filter 103 When the optical filter 103 is used as a near infrared transmission filter, the optical filter 103 preferably satisfies the following (A) and (B).
  • the average transmittance in these wavelength ranges is in this range, visible light can be sufficiently cut when the near infrared transmission filter (optical filter 103) is used as a photoelectric conversion device application, and excellent infrared sensing can be achieved. It is preferable because it can be achieved.
  • the resin layer 102 contains a visible region light absorbing dye having a thermal decomposition start temperature of 150 ° C. or higher.
  • dye is contained in transparent resin with high glass transition temperature. Thereby, the heat resistance of the optical filter 103 can be improved.
  • the configuration of the solid-state imaging device has been described as an example of the configuration of the photoelectric conversion device, but the present invention is not limited to this.
  • the optical filter according to the present invention can be used not only for a solid-state imaging device but also for an illuminance sensor, an ambient light sensor, and the like. The same applies to the configuration 2 of the photoelectric conversion device described later.
  • a base material 101 having a first surface 101a and a second surface 101b is prepared.
  • a light-transmitting substrate is used.
  • a glass substrate or a resin substrate is used as the light-transmitting substrate 101.
  • the thickness of the substrate 101 is preferably 0.01 mm or more and 2 mm or less.
  • the resin composition 104 preferably contains a dye. It is preferable that this pigment
  • dye to be contained in the resin composition 104 differs in the pigment
  • the resin composition 104 preferably contains an inorganic oxide having a function of absorbing infrared light.
  • an inorganic oxide having a function of absorbing infrared light For example, cesium-containing tungsten oxide can be used as the inorganic oxide.
  • the particle size of the inorganic oxide is 200 nm or more and 800 nm or less, preferably 400 nm or more and 700 nm or less.
  • the shape of the inorganic oxide is preferably spherical, but is not limited thereto.
  • the heat treatment is preferably performed at 150 ° C. to 300 ° C.
  • the resin layer 102 can be formed on the first surface 101 a of the base material 101.
  • the resin layer 102 may be peeled off and attached to another substrate.
  • the resin layer 102 can be peeled off and used as a resin base material.
  • the optical filter 103 according to the present embodiment can be formed by the above steps.
  • Resin layer 102 formed as described above has a 10 mN / [mu] m 2 or more 150 mN / [mu] m 2 or less of dynamic hardness. Thereby, the strength of the resin layer 102 can be improved. By forming the resin layer 102 having high strength on the first surface 101a of the base material 101, even if the thickness of the base material 101 is thin, the optical filter 103 is prevented from being broken or chipped off. can do. Further, since the resin layer 102 has high strength, the strength of the optical filter 103 can be maintained without thickening the base material 101. Therefore, the optical filter 103 can be thinned.
  • the heat resistance of the resin layer 102 can be improved by making the resin layer 102 contain the pigment
  • the optical filter 103 according to the present embodiment is held for 60 seconds at 260 ° C. and then cooled to room temperature before and after the reflow test.
  • the rate of change can be 5% or less.
  • the optical filter 103 Due to the high heat resistance of the optical filter 103, the optical filter 103 is deteriorated by heat even in a process having a reflow process in the manufacturing process of the photoelectric conversion device 116 and the camera module 110, and the transmittance fluctuates. Can be prevented.
  • the method of forming the resin layer 102 by applying the resin composition 104 having a polymerizable group on the base material 101 and curing it by heat treatment has been described.
  • the resin layer 102 on the base material 101 by the coating method it can be applied to a large substrate by a simple method compared to the case where the resin layer is formed by the vapor deposition method or the CVD method.
  • the resin layer 102 is formed on the first surface 101a of the base material 101 is shown, but as shown in FIG. 4A, the resin layer 102 is formed on the second surface 101b of the base material 101. May be Further, as shown in FIG. 4B, the resin layer 102 may be formed on both the first surface 101 a and the second surface 101 b of the base material 101. Furthermore, as shown in FIG. 4C, the resin layer 102 may be formed not only on the first surface 101a and the second surface 101b of the base material 101 but also on the side surface.
  • the resin layer 102 By forming the resin layer 102 by a coating method, the resin layer 102 can be easily formed on the side surface of the substrate 101 by a vapor deposition method or a CVD method, as compared to the case where the resin layer 102 is formed. By forming the resin layer 102 also on the side surface of the base material 101, even if light is incident from the side surface of the optical filter 103, infrared light can be cut.
  • the photoelectric conversion device 126 illustrated in FIG. 5 includes a semiconductor substrate 112 provided with the photoelectric conversion element 113, an optical filter 123 provided on the photoelectric conversion element 113, and an optical low pass filter 115.
  • a translucent resin base is used as the optical filter 123 shown in FIG.
  • the resin base is formed using the resin composition described as the resin layer 102 in the previous embodiment.
  • the resin base material can be formed by forming the resin layer 102 on the substrate and peeling the resin layer 102 from the substrate.
  • dye contained in the resin base material it can change suitably by the case where it uses the optical filter 123 for a near-infrared cut off filter, and the case where it uses it for an infrared rays transmission filter.
  • the thickness of the resin substrate is, for example, preferably 200 ⁇ m or less, more preferably 180 ⁇ m or less, still more preferably 150 ⁇ m or less, particularly preferably 120 ⁇ m or less, and the lower limit is not particularly limited. Is desirable.
  • the optical filter 123 can be reduced in weight and size.
  • the thickness of the resin base material is thicker than the above, height reduction of a photoelectric conversion apparatus and a camera module can not be performed.
  • the thickness of the resin base is thinner than the above range, the warpage of the optical filter 123 becomes large.
  • Dynamic hardness of the optical filter 123 that is the resin substrate is preferably 10 mN / [mu] m 2 or more 150 mN / [mu] m 2 or less.
  • the dynamic hardness of the optical filter 123 is in the above range, the strength of the optical filter 123 can be secured. If the dynamic hardness of the optical filter 123 is lower than the above range, the optical filter 123 may be broken or chipped. Moreover, when it is harder than the said range, there exists a possibility that peeling may arise.
  • the dynamic hardness of the optical filter 123 can be measured, for example, with a microhardness tester.
  • the transmittance of the optical filter 103 preferably satisfies the following (A) and (B).
  • (A) The average value of the transmittance in the wavelength range of 430 nm to 580 nm is preferably 75% or more
  • (B) The average value of the transmittance in the wavelength range of 700 nm to 800 nm is 20% or less preferable.
  • the average transmittance in this wavelength range is in this range, near infrared rays can be sufficiently cut when the near infrared cut filter (optical filter 123) is used as a photoelectric conversion device application, and excellent color reproducibility is obtained. It is preferable because it can be achieved.
  • the optical filter 123 has a resin base material containing a dye whose thermal decomposition start temperature is 150 ° C. or more. Moreover, the said pigment
  • the optical filter 123 When the optical filter 103 is used as a near infrared transmission filter, the optical filter 123 preferably satisfies the following (A) and (B).
  • the average transmittance in these wavelength ranges is in this range, visible light can be sufficiently cut when the near infrared transmission filter (optical filter 123) is used as a photoelectric conversion device application, and excellent infrared sensing can be achieved. It is preferable because it can be achieved.
  • the optical filter 123 preferably contains an inorganic oxide having a function of absorbing infrared light.
  • cesium-containing tungsten oxide can be used as the inorganic oxide.
  • the optical filter 123 has a resin base material containing a dye whose thermal decomposition start temperature is 150 ° C. or more. Moreover, the said pigment
  • the pigment it is preferable to contain a green pigment and a black pigment.
  • the green dye is preferably at least one selected from squarylium dyes, phthalocyanine dyes, and cyanine dyes.
  • a dielectric multilayer film may be provided on at least one surface of the above-described resin base material.
  • the manufacturing cost is reduced and the manufacturing process becomes easy.
  • the dielectric multilayer film is provided on both sides of the resin base, it is possible to obtain the optical filter 123 which has high strength and is less likely to be warped or twisted.
  • the optical filter 123 is applied to a photoelectric conversion device or the like, it is preferable to provide a dielectric multilayer film on both sides of the resin base, since it is preferable that the warping and twisting of the optical filter 123 be small.
  • the optical filter 123 has an average transmittance change rate of 5% or less at a wavelength of 700 nm to 1100 nm before and after a reflow test in which an operation of holding at 260 ° C. for 60 seconds and cooling to room temperature is performed. is there. Thereby, even if high temperature is applied in the manufacturing process of the photoelectric conversion device 126 and the camera module 120, it is possible to prevent the optical filter 123 from being deteriorated by heat and fluctuating the transmittance.
  • the camera module 120 also includes a photoelectric conversion device 126, a lens 117, and a package 118.
  • the optical filter 123 and the optical low pass filter 115 are held by the package 118.
  • the package 118 has a region in which the photoelectric conversion device 126 is accommodated, and a lens barrel portion that holds the lens 117, and is fixed to the support substrate 111.
  • the thinned optical filter 123 for the photoelectric conversion device 126, the height of the photoelectric conversion device 126 and the camera module 110 can be reduced.
  • the optical filter 123 and the optical low pass filter 115 the imaging quality of the photoelectric conversion device 126 can be improved.
  • a temperature of about 260 ° C. may be added to the near infrared cut filter. Since the optical filter 123 according to the present embodiment has heat resistance, it is possible to suppress the deterioration of the optical filter 123 in the reflow process.
  • the optical filter 123 according to the present embodiment is reduced in thickness.
  • the optical filter 123 is used for a lens unit such as a camera module, the height and weight of the lens unit can be reduced.
  • An optical filter and a photoelectric conversion device includes a digital still camera, a camera for a mobile phone, a digital video camera, a camera for a personal computer, a surveillance camera, a camera for an automobile, a television, an on-vehicle device for a car navigation system It can be suitably used for portable information terminals, video game machines, portable game machines, devices for fingerprint authentication systems, digital music players, and the like. Furthermore, it can be suitably used also as a heat ray cut filter etc. with which glass etc., such as a car and a building, etc. are equipped.
  • 101 base material
  • 101a first surface
  • 101b second surface
  • 102 resin layer
  • 103 optical filter
  • 104 resin composition
  • 111 support substrate
  • 112 semiconductor substrate
  • 113 photoelectric conversion element
  • 114 Wire
  • 115 Optical low pass filter
  • 116 Photoelectric conversion device
  • 117 Lens
  • 118 Package
  • 120 Camera module
  • 123 Optical filter
  • 126 Photoelectric conversion device

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  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Optical Filters (AREA)
  • Solid State Image Pick-Up Elements (AREA)
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PCT/JP2018/028467 2017-07-31 2018-07-30 光電変換装置 WO2019026848A1 (ja)

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KR102562643B1 (ko) 2023-08-03

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